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Two interesting Cu6Gd3 and Cu5Dy2 cluster has been synthesized. Cu6Gd3 shows magnetocaloric properties and zero field SMM behaviour is prevalent for Cu5Dy2. A comparative study on anticancer activity, DNA and protein binding has also been performed.

A new mononuclear copper(II) complex [Cu(HL)2] (1), has been synthesized from a Schiff base ligand (H2L) and characterized by FTIR spectroscopy, UV-Vis spectroscopy, single crystal X-ray diffraction, and powder X-ray...

Nucleophilic addition to p-benzynes derived via Bergman cyclization has become a topic of keen interest. Studying the regioselectivity in such addition can reveal important information regarding the parameters controlling such addition. Recently, high regioselectivity has been achieved in nucleophilic addition to a p-benzyne derived from an ortho substituted benzo fused cyclic azaenediyne. Rather than having a freely rotating substitution, a rigid hydrogen atom coming from a suitable naptho fused enediyne and residing in the plane of the p-benzyne ring can offer hindrance to the trajectory of the nucleophile. This can lead to regioselectivity provided the other side remains relatively free of such hindrance. Based on that approach, halide addition to p-benzynes derived from naphtho fused cyclic azaenediynes was studied and a high level of regioselectivity was observed. Steric hindrance to the trajectory of nucleophile by the bay hydrogen was found to be the main cause of such regioselectivity; however, differential electrostatic potential as well as distortions at reactive centres have a minor role in controlling the regioselectivity. The products of such high yielding addition are the halo naphtho tetrahydroisoquinolines.

The design and synthesis of a Schiff base H2L, (2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol), bearing an ONOO donor set has been explored for its reactivity pattern with LnCl3·6H2O (Ln = GdIII and DyIII) and Ni(CH3CO2)2·4H2O in the presence of NEt3 for molecular aggregation. Coordination driven spontaneous self-assembly reactions provide [Gd2Ni6L4(μ3-OH)6(μ-OH)2(CH3CO2)2(μ-H2O)2(H2O)3(MeOH)]·8H2O (1) having a ‘butterfly-shaped’ core and [Dy2Ni6L4(μ3-OH)4(μ-Cl)2Cl4(H2O)2(MeOH)2]·2MeOH·4H2O (2) with a ‘candy-shaped’ core. Fusion of six partial cubane units led to a mineral-like core in 1, developed around the central Ni2(OH)2 moiety, whereas in the case of 2, four such partial cubanes collapsed on Dy2(OH)2. Direct-current (dc) magnetic susceptibility measurements revealed that predominant ferromagnetic interactions lead to a high-spin S = 13 ground state for 1. Complex 2 exhibits slow relaxation of magnetization under an applied small dc field with an energy barrier to reorientation of the magnetization, Ueff = 19.3 K. The static and dynamic magnetic data are analysed and corroborated by density functional theory (DFT) and detailed CASSCF based calculations.

Five new cobalt(ii/iii)-lanthanide(iii)-based coordination aggregates, [LnIII3CoII2CoIII2(L1)2(O2CCMe3)8(OH)4(OMe)2(H2O)4]·Ln(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·2MeOH·2H2O (where Ln = Tb (1), Ho (3), and H2L1 = N-(2-hydroxyethyl)-salicylaldimine), TbIII3CoII3CoIII4(L1)4(O2CCMe3)9(OH)10(H2O) (4) and LnIII3CoII2CoIII5(L1)4(O2CCMe3)10(OH)10 (Ln = Dy (5), Ho (6)) have been synthesized and characterized, including structural analysis via single-crystal X-ray diffraction. The dysprosium analogue (2) of 1 and 3 was previously reported by us. The heptanuclear monocationic clusters in 1 and 3 were formed by placement of seven metal ions (4 Co and 3 Ln) in a vertex shared dicubane structure from the control of two Schiff base anions and crystallized in the presence of in situ generated and literature unknown counter anions Tb(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2- and Ho(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2-. Interesting solvent-induced cluster structure transformation was observed on dissolving the heptanuclear aggregates in MeCN for the formation of decanuclear clusters 4-6. These high nuclearity clusters consist of a vertex shared heptanuclear dicubane part and a curved trinuclear chain linking the two cubic halves. The dicubane unit differs from that of the heptanuclear precursors in the presence of CoII/III at the shared vertex as opposed to LnIII and the absence of OMe- bridges. HRMS (+ve) analysis shed light on the pathway of formation of these heptanuclear molecules, while at the same time revealing a different aggregation process for the decanuclear clusters.

Two new families of cobalt(II/III)–lanthanide(III) coordination aggregates have been reported: tetranuclear [LnIII2CoIII2L2(N-BuDEA)2(O2CCMe3)4(H2O)2]·(MeOH)n·(H2O)m (Ln = Gd, 1; Tb, 2; Dy, 3; n = 2, m = 10 for 1 and 2; n = 6, m = 2 for 3) and pentanuclear LnIII2CoIICoIII2L2(N-BuDEA)2(O2CCMe3)6(MeOH)2 (Ln = Dy, 4; Ho, 5) formed from the reaction of two aggregation assisting ligands H2L (o-vanillin oxime) and N-BuDEAH2 (N-butyldiethanolamine). A change in preference from a lower to higher nuclearity structure was observed on going across the lanthanide series brought about by the variation in the size of the LnIII ions. An interesting observation was made for the varying sequence of addition of the ligands into the reaction medium paving the way to access both structural types for Ln = Dy. HRMS (+ve) of solutions gave further insight into the formation of the aggregates via different pathways. The tetranuclear complexes adopt a modified butterfly structure with a more complex bridging network while trapping of an extra CoII ion in the pentanuclear complexes destroys this arrangement putting the Co–Co–Co axis above the Ln–Ln axis. Direct current (dc) magnetic susceptibility measurements reveal weak antiferromagnetic coupling in 1. Complexes 2 and 5 display no slow magnetic relaxation, whereas complexes 3 and 4 display out-of-phase signals at low temperature in ac susceptibility measurements. All compounds were analyzed with DFT and CASSCF calculations and informations about the single-ion anisotropies and mutual 4f–4f/4f–3d magnetic interactions were derived.

The versatility for a unique aggregation of heterometallic 3d-4f and 3d-3d'-4f ions by the new Schiff base ligand 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol (H2L) providing O3N donors has been examined. A series of complexes having the general formula [Ln2Ni4(L)4(μ1,3-CH3CO2)2(μ3-OH)4(MeOH)2]·xCH3OH·yH2O [where Ln = DyIII, x = 4, y = 0 (1), Ln = TbIII, x = 0, y = 4 (2), and Ln = HoIII, x = 4, y = 0 (3)] were obtained from the sequential use of lanthanide(III) nitrate salts and Ni(CH3CO2)2·4H2O. The incorporation of two different 3d ions and one 4f ion in the same coordination aggregate was achieved through the isomorphic replacement of two NiII centers by MnIII ions as second group of cationic complexes, [Ln2Ni2Mn2(L)4(μ1,3-CH3CO2)2(μ3-OH)4(MeOH)2](NO3)2·2CH3OH [where Ln = DyIII (4), TbIII (5), and HoIII (6)]. Direct-current (dc) magnetic susceptibility studies hint to the possibility of ferromagnetic interactions occurring in the aggregates, whereas alternating-current susceptibility measurements find both the DyIII analogues, 1 and 4, to show out-of-phase components at zero applied dc field, characteristic of single-molecule-magnet (SMM) behavior. Micro-SQUID studies reveal open hysteresis loops for 1, corroborating its SMM character. Further detailed complete-active-space self-consistent-field and density functional theory calculations were also performed, supporting the experimental findings in complexes 1 and 4.

A family of 3d-4f aggregates have been reported through guiding the dual coordination modes of ligand anion (HL- ) and in situ generated ancillary bridge driven self-assembly coordination responses toward two different types of metal ions. Reactions of lanthanide(III) nitrate (Ln=Gd, Tb, Dy, Ho and Yb), nickel(II) acetate and phenol-based ditopic ligand anion of 2-[{(2-hydroxypropyl)imino}methyl]-6-methoxyphenol (H2 L) in MeCN-MeOH (3 : 1) mixture and LiOH provided five new octanuclear Ni-4f coordination aggregates from two Ni2 Ln2 cubanes. Single-crystal X-ray diffraction analysis reveals that all the members of the family are isostructural, with the central core formed from the coupling of two distorted [Ni2 Ln2 O4 ] heterometallic cubanes [Ni2 Ln2 (HL)2 (μ3 -OH)2 (OH)(OAc)4 ]+ (Ln=Gd (1), Tb (2), Dy (3), Ho (4) and Yb (5)). Higher coordination demand of 4f ions induced the coupling of the two cubes by (OH)(OAc)2 bridges. Variable temperature magnetic study reveals weak coupling between the Ni2+ and Ln3+ ions. For the Tb (2) and Dy (3) analogs, the compounds are SMMs without an applied dc field, whereas the Gd (1) analogue is not an SMM. The observation revealed thus that the anisotropy of the Ln3+ ions is central to display the SMM behavior within this structurally intriguing family of compounds.

The synthesis, structural characterization, and magnetic behavior of a new family of binuclear CoII–LnIII complexes of formula [LnIIICoIIL2(NO3)3]·H2O (Ln = La, 1; Gd, 2; Tb, 3; Dy, 4; Ho, 5; HL = ...

A family of tetranuclear Ni-4f coordination aggregates (CAs) from the support of a carbazido ligand is described. The option of altering the 4f ions during synthesis within the family, without altering the core topology, gave the four members of the family. Tetranuclear (2 : 2) heterometallic compounds [NiII2LnIII2(μ3-L)2(μ3-OH)2(μ-OAc)3(AcO)(H2O)3]Cl2·4H2O (Ln = Gd, 1; Tb, 2; Dy, 3; Ho, 4) have been assembled through the utilization of all the coordination sites of the anionic form of 1-(2-hydroxy-3-methoxybenzylidene)semicarbazide (HL) and bridging supports from HO− and AcO− ions. The four metal ion centers of two different types, are held together by two μ-L−, two μ3-HO− and three μ1,3-AcO− bridges to self-assemble into Ni2Ln2O4 hetero-cubane structures. In each cube, LnIII ions are linked by two hydroxido and one phenoxido bridge and each NiII ion is linked by two phenoxido and one hydroxido bridge, so that each hydroxido group in μ3-mode is linked to two LnIII and one NiII and each phenoxido ion in μ3-mode is linked to two NiII and one LnIII. Variable temperature magnetic properties have been examined to find the role of magnetic anisotropy for the single molecule magnet (SMM) behavior. All of them show large ground state magnetic moment values and absence of out-of-phase ac susceptibility signals. The absence of SMM behavior is ascribed to the lack of axial magnetic anisotropy.

A family of four isostructural [Ln

One-pot reactions of an asymmetric carboxy-ether-phenol based Schiff base H

Simultaneous incorporation of both CoII and CoIII ions within a new thioether S-bearing phenol-based ligand system, H3 L (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) formed [Co5 ] aggregates [CoII CoIII 4 L2 (μ-OH)2 (μ1,3 -O2 CCH3 )2 ](ClO4 )4 ⋅H2 O (1) and [CoII CoIII 4 L2 (μ-OH)2 (μ1,3 -O2 CC2 H5 )2 ](ClO4 )4 ⋅H2 O (2). The magnetic studies revealed axial zero-field splitting (ZFS) parameter, D/hc=-23.6 and -24.3 cm-1 , and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with Ueff /kB =30 K (1) and 33 K (2), and τ0 =9.1×10-8 s (1), and 4.3×10-8 s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central CoII centers, thus affecting the D and Ueff /kB values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {CoIII 2 (μ-L)} units, display solvent-dependent catechol oxidation behavior toward 3,5-di-tert-butylcatechol in air. The presence of an adjacent CoIII ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.

New Schiff base ligand H2L containing N2O4S donor atoms has been explored for its ability to provide complexes of selected 3d and 4f metal ions. Room temperature reaction of H2L with NiCl2·6H2O and Ln(NO3)3·5H2O in the presence of Et3N in MeCN-MeOH (2:1) medium resulted in [Ni4Ln2(L)2(μ-Cl)2(μ3-OH)4(H2O)6]Cl4·2H2O (where Ln = Dy3+ (1), Tb3+ (2), and Ho3+ (3) and H2L = 2-((2-(2-(2-hydroxy-3-methoxybenzylideneamino)ethylthio)ethylimino)methyl)-6-methoxyphenol). Use of Ni(SCN)2·4H2O during synthesis provided SCN- ions for bridging and terminal coordination in [Ni4Ln2(L)2(μ-NCS)2(μ3-OH)4(NCS)4(H2O)2]·xMeOH·yH2O (where Ln = Dy3+ (4), x = 2, y = 4; Tb3+ (5) and Ho3+ (6), x = 0, y = 14.1). All six complexes possess a hexanuclear defective tetracubane topology having exchangeable bridging groups. The study of direct current magnetic susceptibility measurements revealed that the Ni(II) ions are engaged in ferromagnetic interaction with the DyIII, TbIII, and HoIII ions and have significant magnetic anisotropy in all six complexes. Alternating current susceptibility measurements confirmed that both of the two types of compounds qualify as zero-field single-molecule magnets (SMMs), and the effective barrier for the reversal of the magnetic moment was found to be in the range Ueff = 23-31 K for 1-2 and 4-5, respectively. Detailed insight into the electronic structure and magnetic properties was calculated using DFT- and CASSCF-based analyses. The found isotropic exchange parameter (J) values are JNi-Ni = -4.7 cm-1 for 1 and JNi-Ni = +29.2 cm-1 for 4 and clearly indicate that the μ-NCS-bridge is a better candidate than μ-Cl for ferromagnetic exchange interactions. Out of the six complexes, only complex 5 displays TbIII centered emission peaks at 451 and 480 nm.

Linear and flexible N4 ligand trien (N′-{2-(2-aminoethylamino)-ethyl}-ethane-1,2-diamine) has been used to show octahderal coordination around NiII ions and cis coordination from two ancillary bridges from azide ions. Room temperature reaction of trien with Ni(NO3)·6H2O and NaN3 has led to an end-to-end (EE) azido bridged one-dimensional NiII based helical coordination chain of formula [NiII(μ-N3)2 (trien)]n (NO3)·H2O {1n·(NO3)·H2O}. Propagation of the chain in one dimension in a helical fashion is continued from the azido bridges in cis directions. Comparative reaction protocol using Co(NO3)2·6H2O on the other hand provided a discrete mononuclear octahedral cobalt (III) complex cis-[CoIII(N3)2 (trien)](NO3)·2H2O {2·(NO3)·2H2O} due to different type of ligand wrapping having only terminal coordination from azide ions.

The dinuclear copper(II) complex [Cu2(µ–L2NH)2(OH2)2](ClO4)4 (1) was obtained following one imine side arm hydrolysis of HL1 (2,6-bis-[{3-(diethylamino)propylimino}methyl]-4-methylphenol). Introduction of carboxylates inhibited the hydrolysis and resulted in two tetranuclear copper(II) complexes [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CCH3)4]·H2O (2a) and [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CC2H5)4]·H2O (2b). Use of perchlorate and carboxylate salts of copper(II) for the reactions under study with HL1 has directed these reactions. Perchlorate anions in presence of H2O molecules, as hydrolytic nucleophiles, triggered imine arm hydrolysis and bridging carboxylate anions allowed transformation of copper(II) bound H2O molecule to μ4-oxido central nucleating group via hydroxido-bridge. The complexes were obtained from simultaneous chelation and bridging by the hydrolyzed and as used ligand anions L2NH− and HL1− respectively. These complexes have been characterized in the solid state by X-ray crystallography and FT-IR spectroscopy. Solution phase stability of Cu2-based fragments was studied by UV–vis absorption spectroscopy. Solution properties have been examined for substrate binding in catechol oxidase activity and binding affinity for biomacromolecules like DNA and Human Serum Albumin.

Rational ligand design approaches allowed {Cu2(μ-OH/OMe)} cores to be accommodated within μ-phenoxido bis(tetradentate) and μ-phenoxido bis(tridentate) ligands having thioether donors. The complexes [Cu2(μ-H2L1)(μ-OH)](ClO4)2·2H2O (1), [Cu2(μ-L2)(μ-OH)(OH2)](ClO4)2 (2a) and [Cu2(μ-L2)(μ-OCH3)(OH2)](ClO4)2 (2b) were obtained from an N2O3S2 donor set bearing the H3L1 ligand (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) and N2OS2 donor set containing the HL2 ligand (4-methyl-2,6-bis-[{2-(methylthio)phenylimino}methyl]phenol) without showing double phenoxido bridging or any type of preformed inter-fragment aggregation. Previously, we showed that H3L (2,6-bis[((2-(2-hydroxyethoxy)ethyl)imino)methyl]-4-methylphenol), the ether analogue of H3L1, in the presence of carboxylate anions, was responsible for the self-aggregation of preformed {Cu2} fragments and gave two types of [Cu4] complexes comprising [Cu4O] and [Cu4(OH)2] cores (T. S. Mahapatra, A. Bauza, D. Dutta, S. Mishra, A. Frontera and D. Ray, ChemistrySelect, 2016, 1, 64–74). The molecular structures of 1, 2a and 2b were determined via single crystal X-ray diffraction and solution studies, which indicated the presence of [Cu2] species. This was further confirmed via UV-vis spectroscopy and HRMS analysis. The synthesized complexes were screened for their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2). A change in the mechanism of catalytic oxidation was observed with a change in the ligand backbone. All three complexes also showed DNA binding properties, which were further substantiated via molecular docking studies. Their DNA binding affinities were quantitatively ascertained using their intrinsic binding constant, Kb, values which were found to be 4.2 × 104, 5.6 × 104 and 4.8 × 104 M−1, respectively. Furthermore, the complexes displayed efficient DNA cleavage behaviour with pBR322 and the oxidative path was established in presence of ROS, singlet oxygen, 1O2, and the superoxide anion, O2·−.

The design and synthesis of a Schiff base H

The heterometallic bridging potential of the anion of 1-(2-hydroxy-3-methoxybenzylidene)semicarbazide (HL) to CoII and four 4f ions was examined during a 4f ion coordination-driven cleavage of [Co2(μ-OH2)(O2CCMe3)4(HO2CCMe3)4] (Co2-Piv) and scrambling of pivalate anions from the starting material. Room-temperature reactions with four different lanthanide nitrate salts yielded [CoLnL(μ2-OOCCMe3)4(CH3OH)]·3CH3OH [Ln = Gd (1), Tb (2), Dy (3) and Ho (4)]. The formation in solution and the crystallization in the solid state indicated that the reactions inhibit any further aggregation of Co-Ln cores to higher order aggregates. After scrambling, the pivalate ions in [Co-Ln] show three types of coordination modes to sustain the dinuclear aggregates with varying degrees of distortion in the dinuclear entities bound to a single L− ion. Atom economy was maintained with respect to the pivalate ions as no external addition of these anions was made. The dc magnetic measurements revealed the presence of weak ferromagnetic interactions in complexes 1 and 2 and weak antiferromagnetic interactions in complexes 3 and 4.

One-pot reactions of an asymmetric carboxy-ether-phenol based Schiff base H2L (2-((2-hydroxy-3-methoxybenzylidene)amino)benzoic acid) with selected Ln(NO3)3·nH2O and [Co2(μ-OH2)(O2CCMe3)4(HO2CCMe3)4] (Co2-Piv) in basic MeOH medium resulted in a family of three octanuclear complexes, [CoII4LnIII4L4(μ1,3-Piv)4(μ1,1,3-Piv)2(η1-Piv)2(μ3-OH)4(MeOH)2]·mMeOH·nH2O (Ln = Dy; m = 3, n = 1 (1), Ho; m = 4, n = 0 (2), Yb; m = 3, n = 1 (3)). The coordination aggregates thus obtained were nicely sustained by four ligand anions and eight externally added carboxylate anions showing three different modes of intermetallic connectivity. The options for incorporating different 4f ions in an investigative synthesis, without altering the resulting intermetallic core structure, were successful for the three representative examples. Single-crystal X-ray diffraction studies revealed that the compounds are isostructural and built from two initially formed partial dicubane-type Co2Ln2L2 units. In each of the tetranuclear parts, the metal ion centers are held together by two L2-, two μ3-HO-, three Piv- bridges, one terminal Piv-, and one terminal MeOH. Four carboxylate ends of four L2- units are responsible for connecting two Co2Ln2 units into octanuclear structures. The unique distortion around the CoII centers is achieved from the facile coordination of bigger 4f ions to the adjacent hard OO sites. The distortion is further maintained by the presence of terminal COO- groups from L2-. The dc magnetic susceptibility data revealed ferromagnetic coupling between the CoII and LnIII centers within the series, whereas the ac magnetic susceptibility measurements identified only 1, having a highly anisotropic DyIII ion, as a single-molecule magnet in the absence of any external magnetic field, with an energy barrier Ueff of 12.5 K.

The versatility for a unique aggregation of heterometallic 3d-4f and 3d-3d'-4f ions by the new Schiff base ligand 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol (H

A family of 3d-4f aggregates have been reported through guiding the dual coordination modes of ligand anion (HL

The variable coordination behavior of 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}-6-methoxyphenol (H

Three new cobalt(ii/iii)-dysprosium(iii) complexes, [DyIII3CoII2CoIII2(L1)2(O2CCMe3)8(OH)4(OMe)2(H2O)4]·Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·4H2O (1), [DyIII3CoII2CoIII2(L2)2(O2CCMe3)8(OH)4(OMe)2(MeOH)2(H2O)2]·Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2·4MeOH (2) and DyIII2CoII2CoIII2(L2)2(O2CCMe3)10(OH)2 (3) have been reported. In the heptanuclear 3d-4f monocationic aggregates in 1 and 2 the three dysprosium and four cobalt sites are arranged into a vertex shared dicubane structure, induced by two structure-directing ligands. Interestingly, a unique and previously unknown dysprosium(iii)-pivalate based counter anion, Dy(η1-O2CCMe3)2(η2-O2CCMe3)2(MeOH)2-, was trapped by the monocationic cores during crystallization. MeCN induced structural rearrangement of 2 through loss of OMe- bridges and dysprosium(iii) ions at the shared vertex resulted in the hexanuclear 3d-4f neutral aggregate 3, in which two dysprosium and four cobalt sites exhibit a near planar disposition. HRMS(+ve) of solutions of 1 and 2 revealed the pathway for aggregation processes and solvent induced structural transformation along with the importance of bridging OMe- in directing the formation of these compounds. Magnetic studies show a non-zero out-of-phase component in the AC susceptibility measurements of 1 but not in 2 and 3, although 1 and 2 have a very similar {CoIII2CoII2DyIII3} core and another DyIII center. Ab initio single-ion calculations point to the different single-ion anisotropic behavior for DyIII centers (energy in cm-1 and g-tensors) as well as negative and positive D values for CoII sites in 1 and 2 respectively reaffirming the experimental result. However, calculations envision that, zero-field out-of-phase signal and no out-of-phase signal in 1 and 2 respectively do not solely generate from the single-ion Dy/Co anisotropies and the overall relaxation mechanism can be understood by considering the exchange interactions between DyIII-DyIII and DyIII-CoII centres.

A systematic one-step one-pot multicomponent reaction of Co(ClO4)2·6H2O, H3L (2,6-bis((2-(2-hydroxyethylamino)ethylimino)methyl)-4-methylphenol), and readily available carboxylate salts (RCO2Na; R ...

The Schiff base ligand, 2-(((2-hydroxybenzyl)imino)methyl)phenol (H2L) having ONO donor centres are utilized to synthesize {Ni4Dy3} coordination aggregate following the support of six benzoate bridging groups. Sequential addition of Dy(NO3)3·6H2O and NiCl2·6H2O to H2L followed by PhCO2Na completes the coordination driven aggregation of heptanuclear Na[Ni4Dy3(L)4(μ3-OH)4(μ1,1,3,3-PhCO2)2(μ1,3-PhCO2)4(CH3OH)4]∙CH2Cl2·9H2O (1) having 2,3,6M7 − 1 topology. Two adjacent perpendicular inverse Ni2Dy2 partial di-cubane units sharing a common vertex through the central DyIII ion resulted a new structural arrangement within the Ni − Dy family of coordination aggregates. The complex shows no slow magnetic relaxation under zero applied fields and only shows a very weak field dependent magnetization. The DFT calculations revealed weak ferromagnetic exchange between benzoato-bridged NiII ions, whereas the CASSCF calculations were used to identify magnetic anisotropy in NiII and DyIII ions resulting in low-lying excited states of DyIII ions with significant probability for the quantum tunneling of the magnetization, which rationalize the observed fast dynamics in the magnetic properties.

In the present work, a discrete dinuclear cadmium(II) complex Cd2(μ−H2L)(μ−OH)Cl2⋅H2O (1) and a dinuclear zinc(II) based 1D chain complex ({Zn2(L')(O2CCH3)}ClO4⋅3H2O)n (2) (where H3L = 2,6-bis{2-(2-hydroxyethylamino)ethylimino}methyl-4-methylphenol and H2L′ = bis-oxazoline (BOX) ligand), have been synthesized and characterized by single-crystal X-ray crystallography. The Cd2+ ions in the first case showed straight cut incorporation of metal ions within the ligand pockets. In case of zinc(II), the coordination induced oxazolidine ring formation resulted in macrocyclic ligand formation having two adjacent coordination pockets. In complex 2, the acetate ion acts as an O,O linker and joins the Zn2 nodes bound within the newly formed macrocyclic ligand bearing bis-oxazolidine rings to form 1D polymeric chain at the end. The H3L was next screened for its efficacy as selective fluorescence sensor for Mg2+ ions in aqueous MeOH medium. Steady state absorption and emission behaviour of H3L, 1 and 2 have been investigated. Time resolved fluorescence properties of H3L and the complexes 1 and 2 have been examined, and their lifetimes have been determined in 0.038–0.257 ns range. The cell viability in presence of H3L makes it a suitable candidate for application in live cell imaging studies.

Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magne...

This work describes the synthesis of azidonaphthalimide carboxylic acids which act as fluorescent templates with a built-in photoreactive group and a linker thus simplifying the design of protein labeling agents. These were separately connected to selectivity hands like a sulfonamide and ampicillin for successful labeling/detection of HCAII and PBPs, respectively.

Simultaneous incorporation of both Co

Rational ligand design approaches allowed {Cu2(μ-OH/OMe)} cores to be accommodated within μ-phenoxido bis(tetradentate) and μ-phenoxido bis(tridentate) ligands having thioether donors. The complexes [Cu2(μ-H2L1)(μ-OH)](ClO4)2·2H2O (1), [Cu2(μ-L2)(μ-OH)(OH2)](ClO4)2 (2a) and [Cu2(μ-L2)(μ-OCH3)(OH2)](ClO4)2 (2b) were obtained from an N2O3S2 donor set bearing the H3L1 ligand (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) and N2OS2 donor set containing the HL2 ligand (4-methyl-2,6-bis-[{2-(methylthio)phenylimino}methyl]phenol) without showing double phenoxido bridging or any type of preformed inter-fragment aggregation. Previously, we showed that H3L (2,6-bis[((2-(2-hydroxyethoxy)ethyl)imino)methyl]-4-methylphenol), the ether analogue of H3L1, in the presence of carboxylate anions, was responsible for the self-aggregation of preformed {Cu2} fragments and gave two types of [Cu4] complexes comprising [Cu4O] and [Cu4(OH)2] cores (T. S. Mahapatra, A. Bauzá, D. Dutta, S. Mishra, A. Frontera and D. Ray, ChemistrySelect, 2016, 1, 64-74). The molecular structures of 1, 2a and 2b were determined via single crystal X-ray diffraction and solution studies, which indicated the presence of [Cu2] species. This was further confirmed via UV-vis spectroscopy and HRMS analysis. The synthesized complexes were screened for their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2). A change in the mechanism of catalytic oxidation was observed with a change in the ligand backbone. All three complexes also showed DNA binding properties, which were further substantiated via molecular docking studies. Their DNA binding affinities were quantitatively ascertained using their intrinsic binding constant, Kb, values which were found to be 4.2 × 104, 5.6 × 104 and 4.8 × 104 M-1, respectively. Furthermore, the complexes displayed efficient DNA cleavage behaviour with pBR322 and the oxidative path was established in presence of ROS, singlet oxygen, 1O2, and the superoxide anion, O2·-.

The bridging nature of in situ generated hydroxide ions and carboxylates (RCOO(-); R = CH3, C2H5, CH2Ph) has been utilized to design a new family of [Cu6] coordination complexes: [Cu6(μ3-OH)2(μ-H2L)2(μ1,1,3-O2CCH3)2(μ1,3-O2CCH3)2(μ-ClO4)2](ClO4)2·H2O (), [Cu6(μ3-OH)2(μ-H2L)2(μ1,1,3-O2CC2H5)4(μ-ClO4)2](ClO4)2·2H2O () and [Cu6(μ3-OH)2(μ-H2L)2(μ1,3-O2CCH2Ph)4(ClO4)2](ClO4)2·2H2O (). Tetracarboxylate bridged {Cu2} core units are trapped between two ligand-bound {Cu2(μ-H2L)(μ-OH)}(2+) subunits forming the [Cu6] complexes. The hexanuclear {Cu6(μ3-OH)2(H2L)2(μ-O2CR)4}(4+) cores having six interconnected Cu(II) ions assume a hitherto unknown dumbbell-shaped topology. Detailed characterizations have been done using X-ray crystallography and variable temperature magnetic measurements. For complexes , the dominant coupling constant (J') values between carboxylate bridged copper centers are -36.2 to -45.2 cm(-1) for short CuCu separations of 2.540-2.578 Å. In MeCN solutions all three complexes showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) in air.

The reaction of three copper(II) carboxylate (R = Me, Ph and H in RCO2−) salts in MeOH with H3L resulted three [Cu4] aggregates: [Cu4(μ4-O)(μ-H2L)2(μ1,3-O2CCH3)4] (1), [Cu4(μ4-O)(μ-H2L)2(μ1,3-O2CPh)(PhCO2)3]⋅H2O (2⋅H2O), and [Cu4(μ3-OH)2(μ-H2L)2(μ1,1-HCO2)2(HCO2)2]⋅2H2O (3⋅2H2O). Three different carboxylate groups showing varying coordination modes were responsible for the self-aggregation of two ligand bound [Cu2(H2L)]3+ units. The [Cu4O] and [Cu4(OH)2] cores were generated from water-derived oxido and hydroxido nucleating groups to provide quasi-tetrahedral and partial-dicubane topologies. In complexes 1 and 2⋅2H2O the μ1,3 bridging mode of the carboxylate bridges were responsible for the entrapment of μ4-O unit, whereas μ1,1 bridge by formato groups resulted in trapping of two μ3-OH units in complex 3⋅2H2O. Complex 3⋅2H2O is the first reported example of a μ1,1-formato bridged [Cu4] aggregate. Long range van der Waals forces, in presence of hydrogen bonding interactions, also play significant role in the [Cu4] aggregation process. These have been analyzed by DFT calculations and Hirshfeld surface analysis.

Unique dependence on the nature of metal salt and reaction conditions for coordination assembly reactions of varying architecture and nuclearity have been identified in V-shaped [Co3L4] and planar disc-like [Co7L6] compounds: [CoII3L2(μ-L)2(μ-OH2)2(CF3CO2)2] (1) and [CoII7(μ-L)6(μ-OMe)6]Cl2 (2) (HL = 2-{(3-ethoxypropylimino)methyl}-6-methoxyphenol). At room temperature varying reaction conditions, cobalt-ligand ratios and use of different bases allowed unique types of coordination self-assembly. The synthetic marvel lies in the nature of aggregation with respect to the two unrelated cores in 1 and 2. Complex 1 assumes a V-shaped arrangement bound to L−, water and a trifluoroacetate anion, while 2 grows around a central CoII ion surrounded by a {CoII6} hexagon bound to methoxide and L−. Magnetic measurements revealed that the intermetallic interactions are antiferromagnetic in nature in the case of complex 1 and ferromagnetic in the case of 2 involving high spin cobalt(II) ions with stabilization of the high-spin ground state in the latter case. In MeCN solutions complexes 1 and 2 showed catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in air. The kinetic study in MeCN revealed that with respect to the catalytic turnover number (kcat) 2 is more effective than 1 for oxidation of 3,5-DTBCH2.

Schiff base ligand HL has been utilized to build up a new family of five [Ni2] complexes, [Ni2(μ-L)(μ-OH)](ClO4)2 [1(ClO4)2], [Ni2(μ-L)(μ-CF3CO2)2(C3H7NO)(H2O)]CF3CO2·H2O [2a(CF3CO2)·H2O], [Ni2(μ-L)(μ-CH3CH2CO2)2(C3H7NO)(H2O)]ClO4·C3H7NO [2b(ClO4)·C3H7NO], [Ni2(μ-L)(μ-CH3CO2)(μ-NCS)(NCS)(C3H7NO)] (3a) and [Ni2(μ-L)(μ-CH3CO2)(μ-N3)(N3)(C3H7NO)] (3b), in varying co-ligand environments. All the complexes have been characterized by elemental analyses, X-ray structure analysis and spectroscopic measurements. Three distinct types, dicationic, monocationic and neutral complexes, are synthesized using one pentadentate ligand HL. The NiII centers are bridged by three sets of bridging groups resulting in a wide variation in Ni⋯Ni separations from 2.897 to 3.475 A. Doubly bridged NiII centers in the edge-shared square planar environment provide the shortest Ni⋯Ni separation in 12+. Whereas combination of other bridges from carboxylate, azide and isothiocyanate ancillary ligands results in cationic and neutral [Ni2] complexes 2+ and 3 having longer intermetallic separations. Modulation of Ni⋯Ni separation in synthetic complexes is fascinating in relation to the involvement and stabilization of the dinickel motif in the catalytic transition state of urease. Interaction and binding of cationic complexes (1–2b) with human serum albumin (HSA) and calf thymus-DNA have been examined using spectroscopic techniques. Tryptophan fluorescence quenching of HSA by cationic bimetallic complexes (1, 2a and 2b) featuring a hydrophobic ligand environment shows spontaneous and favorable interactions in the order of 2a > 2b > 1. For the interaction study with CT-DNA, nearly planar complex 1 binds more efficiently than 2a and 2b in octahedral coordination geometry.

Two new tetranuclear CuII complexes [Cu4(L2)2(µ2-OH)2(H2O)2]·(ClO4)2·DMF·2H2O (1) and [Cu4(L3)2(µ2-OH)2(H2O)2]·(ClO4)2·DMF·H2O (2) have been synthesized containing piperazine based Schiff base ligands H2L2 (asymmetric) and H2L3 (symmetric). H2L2 contains one o-vanillin and a salicylaldehyde unit while H2L3 has two o-vanillin units. An interesting synthetic methodology involving transition metal ion induced aldehyde exchange reaction between two Schiff base ligands has been explored for the synthesis of H2L2 and H2L3. While the latter can be obtained by direct condensation of the respective amine and aldehyde, the former can only be synthesized by this procedure developed. Both 1 and 2 contain a piperazine ring bridging two CuII centers in chair conformation in the rare axial-equatorial mode of coordination. Two piperazine bridged Cu2 moieties are further connected via two hydroxido and two phenoxido bridges. Of the two Ophenoxido–Cu bonds one is short (basal) and the other is long (apical) while the hydroxido O bridges the two CuII centers symmetrically in basal–basal manner giving rise to a unique [Cu2O2] moiety where, of the four bonds linking the metals, three are basal (short) and one axial (long). Magnetic studies reveal weak antiferromagnetic interactions across the two piperazine bridges with an average exchange constant value of −4.007 cm−1 and −4.507 cm−1 for 1 and 2 respectively. The antiferromagnetic exchanges across the phenoxido–hydroxido bridges were found to be stronger with the average value being −43.036 cm−1 for 1 and −38.031 cm−1 for 2. Computational studies further support the experimental findings and the spin density plots in the HS configuration reveal that the exchange across the piperazine bridge takes place via through space mechanism. The spin density analysis in the HS and BS configurations also reveal that the exchange interaction is propagated mainly through the hydroxido bridge. The unsymmetrical nature of H2L2 leads to greater spin density at the hydroxido bridge in 1 leading to slightly stronger exchange interaction.

The Schiff base ligand HL1 ({2,6-bis(allylimino)methyl}-4-methylphenol) having no coordinating donor arm has been examined for its reaction medium and ancillary bridge dependent reactivity for a hierarchical family of CuII complexes. The ligand showed a unique reactivity pattern toward CuII in solution. The bridging nature of in situ generated HO- ions in the absence and presence of externally added carboxylates (RCOO-; R = CF3, C6H5 and CH3) has been utilized to produce complexes {[Cu2(μ-L2)2(H2O)]2[Cu2(μ-L2)2(H2O)2](ClO4)6} (1) (HL2 = 3-{(allylimino)methyl}-2-hydroxy-5-methylbenzaldehyde), [Cu4(μ4-O)(μ-L1)2(μ1,3-O2CCF3)4] (2), [Cu4(μ4-O)(μ-L1)2(μ1,3-O2CC6H5)4]·H2O (3), and [Cu5(μ3-OH)2(μ-L1)2(μ1,3-OAc)2(OAc)2(H2O)4][Cu5(μ3-OH)2(μ-L1)2(μ1,3-OAc)2(OAc)3(H2O)](ClO4)3·2C2H5OH (4). The absence of carboxylate anions did not yield HO- ions in situ and triggered single ligand arm hydrolysis. The formation of tetra- and pentanuclear aggregates as well as ligand hydrolyzed dinuclear products has been rationalized to identify the possible roles of carboxylate anions in solution. Detailed characterization of the complexes in the solid state and in solution has been carried out using spectroscopic measurements, X-ray crystallography, variable temperature magnetic measurements and functional behavior. In MeOH solutions at 298 K, the complexes 1-4 showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) saturated with O2 from the air.

A systematic one-step one-pot multicomponent reaction of Co(ClO

International audience; Distorted [Cu4(m3-OH)2] cubane type arrangements, one tetracationic and one neutral, have been achieved as [Cu2(m-H2bpmp)(m3OH)(H2O)]2(SO4)2.3H2O.CH3OH (1) and [Cu2(m-Hbpmp)(m3-OH) (m1,3-O2CCF3)]2.H2O.2CF3CO2H (2) [H3bpmp = 2,6-bis-[(3 hydroxypropylimino)methyl]-4-methylphenol] from the reactions of H3bpmp with CuSO4.5H2O and Cu(CF3CO2)2.xH2O in the presence of NEt3in MeOH medium. Two types of apical interactions of the CuII ion with H2O and CF3CO2. induced hydroxido- bridge supported aggregation of {Cu2} precursors. In MeOH solution, the reaction of 1 with CF3CO2. resulted in 2, showing a ligand-exchange reaction, leading to different Cu...O separations in the space on the open faces of the cubane structure. Magnetic susceptibility measurements (1.8–350 K) revealed stronger antiferromagnetic interactions in 1, where the average in plane Cu–O–Cu angle is 100.4°, than for 2, having a smaller Cu–O–Cu angle of 97.2°.

The phenoxido-bridged [Cu-2] complex [Cu-2(-H(4)L1)(-OH)((1,3)-NO3)(NO3)(OH2)]H2O (1) and its hierarchical [Cu-4] and [Cu-5] assemblies [Cu-4(-H(4)L1)(2)(-OH)(2)((1,3)-ClO4)(OH2)(2)](ClO4)(3)2H(2)O (2) and [Cu-5(-H(4)L1)(2)((3)-OH)(2)((1,3)-O2CCF3)(2)(O2CCF3)(2)](CF3COO)(2) (3) were obtained from the reactions of H(5)L1 (2,6-bis-\(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl\-4-methylphen ol) with three copper(ii) salts. The available NO3-, ClO4- and CF3COO- ions have been trapped for spontaneous' anion-directed self-assembly' reactions. All the synthesized complexes contain the [Cu-2(-H(4)L1)(-OH)](2+) fragment, prone to assemble and crystallize [Cu-4] and [Cu-5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3- to ClO4- and CF3COO- results in different courses of reactions based on Cu-2(-H(4)L1) fragments. Binding of NO3- provided 1 as an isolated [Cu-2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the (1,3)-binding mode, has been realized as a solitary support for the condensation of two Cu-2(-H(4)L1) fragments. The \Cu-5((3)-OH)(2)((1,3)-O2CCF3)(2)\(6+) constellation in 3 contains five Cu-II centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (-H(4)L1(-)). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.

The coordination reactivity of ligand H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) toward nickel(II) ions in the presence of two different anions resulted in cubane and fused dicubane types of tetranuclear coordination aggregates. In the first case, utilization of two carboxylate (R = Me and Et in RCO2−) anions led to cubane type Ni4O4 aggregates [Ni4(H4L1)2(μ3-OH)2(μ1,3-O2CCH3)2](NO3)(CH3COO)·3H2O (1) and [Ni4(H4L1)2(μ3-OH)2(μ1,3-O2CC2H5)2](NO3)(C2H5COO)·CH3CN·1.5H2O (2). Whereas the use of thiocyanate anions triggered single imine arm hydrolysis of H5L1 and gave partial dicubane type Ni4N2O4 aggregates [Ni4(H2L2)2(HAMP)2(μ1,1-NCS)2](NO3)2 (3a) and [Ni4(H2L2)2(HAMP)2(μ1,1-NCS)2]Cl2·CH3OH·H2O (3b) (H2L2 = 3-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-2-hydroxy-5-methylbenzaldehyde). Liberated 2-amino-2-methyl-1,3-propanediol from imine arm hydrolysis was successfully trapped in 3a and 3b for the growth and stabilization of different molecular architectures. Mass spectral evidence established that two types of dinuclear fragments Ni2(H4L1) and Ni2(H2L2), from the originally used and partially hydrolyzed ligand anions have been self-assembled for two types of NiII based coordination aggregates. Two sets of complexes were characterized by elemental analysis, FT-IR and optical spectroscopy, variable temperature magnetic measurements, and single crystal X-ray analysis. The magnetic behavior examined through the temperature interval of 1.9–300 K with experimental and theoretical corroboration support the exchange pathways within the two types of [Ni4] coordination aggregates.

The Schiff base ligand HL1 ({2,6-bis(allylimino)methyl}-4-methylphenol) having no coordinating donor arm has been examined for its reaction medium and ancillary bridge dependent reactivity for a hierarchical family of CuII complexes. The ligand showed a unique reactivity pattern toward CuII in solution. The bridging nature of in situ generated HO- ions in the absence and presence of externally added carboxylates (RCOO-; R = CF3, C6H5 and CH3) has been utilized to produce complexes {[Cu2(μ-L2)2(H2O)]2[Cu2(μ-L2)2(H2O)2](ClO4)6} (1) (HL2 = 3-{(allylimino)methyl}-2-hydroxy-5-methylbenzaldehyde), [Cu4(μ4-O)(μ-L1)2(μ1,3-O2CCF3)4] (2), [Cu4(μ4-O)(μ-L1)2(μ1,3-O2CC6H5)4]·H2O (3), and [Cu5(μ3-OH)2(μ-L1)2(μ1,3-OAc)2(OAc)2(H2O)4][Cu5(μ3-OH)2(μ-L1)2(μ1,3-OAc)2(OAc)3(H2O)](ClO4)3·2C2H5OH (4). The absence of carboxylate anions did not yield HO- ions in situ and triggered single ligand arm hydrolysis. The formation of tetra- and pentanuclear aggregates as well as ligand hydrolyzed dinuclear products has been rationalized to identify the possible roles of carboxylate anions in solution. Detailed characterization of the complexes in the solid state and in solution has been carried out using spectroscopic measurements, X-ray crystallography, variable temperature magnetic measurements and functional behavior. In MeOH solutions at 298 K, the complexes 1-4 showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) saturated with O2 from the air.